Effect of composition and temperature variations on thermophysical properties of binary and ternary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate with 1-butanol and/or methanol
Introduction
Ionic liquids (ILs) have attracted the attention of researchers during the last few years owing to their large variety of chemical and technological applications. The interest of a number of research groups has been focused on thermophysical properties of mixtures containing ionic liquids [1], [2], [3]. ILs are usually composed of organic cations and organic/inorganic anions [4], [5]. The most attractive features of ILs are their wide liquid range, negligible vapor pressure and high electrical conductivity, as well as the ability to tune their physicochemical properties by varying the ion structure; the latter has led to their being known as “designer” solvents [6], [7], [8], [9], [10]. The properties such as good thermal stability, high ionic conductivity, good solvation ability, and a wide electrochemical window, make ionic liquids potential novel materials for a wide range of uses, including uses as solvents or catalysts for reactions, lubricants, heat transfer fluids, electrolytes in batteries, capacitors, fuel, and solar cells and media for gas absorption and for liquid separation processes [11], [12], [13], [14], [15], [16]. Thermophysical properties are of utmost importance for the design of new ionic liquids to meet specific requirements. Since the variation of ion pairs gives rise to a great number of ionic liquids with a wide variety of properties, an understanding of solute-solvent interactions is helpful in designing the new IL [17], [18], [19]. In spite of the importance and applicability of ionic liquids and molecular solvents mixtures, the accurate and extensive studies of their fundamental physical and chemical properties are scarce. Studies on physical and chemical properties of ionic liquids, property measurement methodology, high-quality data on reference systems, standards for reporting thermodynamic data and the creation of a comprehensive database have been promoted by NIST [20], IUPAC [21] and DDB (the Dortmund Data Bank) [22]. The studies of thermodynamic and transport properties, like density, speed of sound and viscosity of IL + molecular solvent mixtures are interesting both from practical and theoretical point of view. Moreover, the knowledge of excess properties helps us to understand the structure-property relation, making it easier to search for an optimal ionic liquid for a specific application. One promising ionic liquid 1-ethyl-3-methyl-imidazolium ethylsulfate ([EMIM][ES]) is water-miscible, air-stable, and has a relatively low viscosity [23]. A number of authors have studied the thermophysical properties of pure 1-ethyl-3-methylimidazolium ethylsulfate and its binary and ternary mixtures with organic solvents at different temperatures and at atmospheric pressure [4], [6], [24], [25], [26], [27], [28], [29], [30]. There has not been found any study in literature on the thermophysical properties of binary and ternary mixtures of 1-ethyl-3-methylimidazolium ethyl sulfate with 1-butanol and/or methanol at T = (298.15–323.15) K and at pressure 0.1 MPa.
In this study, the thermophysical properties, densities, speeds of sound and dynamic viscosities of pure 1-ethyl-3-methylimidazolium ethylsulfate, ([EMIM][ES]), 1-butanol, methanol and of their binary mixtures [EMIM][ES] + 1-butanol, [EMIM][ES] + methanol and 1-butanol + methanol and of their ternary mixtures [EMIM][ES] + 1-butanol + methanol have been measured experimentally covering the entire range of composition at temperatures (298.15, 303.15, 308.15, 313.15, 318.15, 323.15) K with an interval of 5 K, and at pressure 0.1 MPa. The excess molar volume (VE), isentropic compressibilities , molar isentropic compressibilities , excess isentropic compressibility (), excess molar isentropic compressibility (), and viscosity deviation (Δη) values have been calculated using the experimental densities, speeds of sound and dynamic viscosities data of pure components and of their binary/ternary mixtures. The experimental VE, and Δη values of binary systems of [EMIM][ES] + 1-butanol, [EMIM][ES] + methanol and 1-butanol + methanol whereas VE, and Δη values of ternary system of [EMIM][ES] + 1-butanol + methanol have been correlated to Redlich-Kister equation [16], [31]. The behavior of excess and deviations properties have been discussed in terms of ion-ion, ion-dipole, dipole-dipole and hydrogen bonding interactions and packing of components in the studied mixtures [24].
Section snippets
Materials
The source, purification method, mass fraction purity and water content of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][ES], 1-butanol and methanol were used in this work are listed in Table 1.
Apparatus and procedure
Water content of pure [EMIM][ES] was measured by Karl Fischer coulometric titrator (C20, Metller Toledo), and was found to be 192 ppm. The binary mixtures, [EMIM][ES] + 1-butanol, [EMIM][ES] + methanol and 1-butanol + methanol and ternary mixture, [EMIM][ES] + 1-butanol + methanol of different mole
Density, speed of sound and viscosity
The measured densities, speeds of sound and viscosities of pure [EMIM][ES], 1-butanol and methanol and of their binary mixtures at the temperatures (298.15, 303.15, 308.15, 313.15, 318.15, and 323.15) K and at 0.1 MPa pressure have been reported in Table 2, Table 3, Table 4, Table 5, respectively. The measured values of densities, speeds of sound and viscosities of pure [EMIM][ES] [6], [24], [25], [26], [27], [28], [29], 1-butanol [32], [33], [34] and methanol [35], [36], [37], [38], [39], [40]
Conclusion
The excess molar volume values have been found to be negative at all composition and temperature and decrease with an increase in temperature for each binary system [EMIM][ES] + 1-butanol, [EMIM][ES] + methanol and 1-butanol + methanol. Similarly, the values have also been found to be negative at all composition and temperature and decrease with an increase in temperature. The Δη values are found to be negative at all composition and temperature and increase with an increase in
Acknowledgements
The authors are thankful to the Chairman Department of Chemistry, A.M.U., Aligarh for providing the necessary facility for the compilation of this work. Financial support from the UGC (Major Research Project) F. No. 41-240/2012(SR) scheme is acknowledged.
References (44)
- et al.
Density and surface tension in binary mixtures of CnMIM-BF4 ionic liquids with water and ethanol
Fluid Phase Equilib.
(2009) Properties of ionic liquid solvents for catalysis
J. Mol. Catal. A
(2004)Recent developments in thermodynamics and thermophysics of non-aqueous mixtures containing ionic liquids. A review
J. Chem. Thermodyn.
(2005)- et al.
Experimental study of the density and viscosity of 1-ethyl-3-methylimidazolium ethyl sulfate
J. Chem. Thermodyn.
(2012) - et al.
Densities, excess volumes, isobaric expansivity, and isothermal compressibility of the (1-ethyl-3-methylimidazolium ethylsulfate + methanol) system at temperatures (283.15 to 333.15) K and pressures from (0.1 to 35) MPa
J. Chem. Thermodyn.
(2008) - et al.
Density and viscosity of 1-butyl-3-methylimidazolium nitrate with ethanol, 1-propanol, or 1-butanol at several temperatures
J. Chem. Thermodyn.
(2009) - et al.
Osmotic and apparent molar properties of binary mixtures alcohol + 1-butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid
J. Chem. Thermodyn.
(2013) - et al.
Evaluation of excess isentropic compressibilities and isochoric heat capacities
J. Chem. Thermodyn.
(1979) - et al.
Ionic liquids in synthesis
Wiley-VCH Weinh.
(2003) - et al.
Surface tension and density of pure ionic liquids and some binary mixtures with 1-propanol and 1-butanol
J. Chem. Eng. Data
(2008)
Density, speed of sound, viscosity, and excess properties of binary mixtures formed by ethanol and bis(trifluorosulfonyl)imide-based ionic liquids
J. Chem. Eng. Data
1-ethyl-3-methylimidazolium ethylsulfate in water, acetonitrile, and dichloromethane: molar conductivities and association constants
J. Chem. Eng. Data
Effect of relative humidity of air on density, apparent molar volume, viscosity, surface tension, and water content of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid
J. Chem. Eng. Data
Thermophysical properties of 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethane-sulfonate and 1-ethyl-3-methylimidazolium ethylsulfate ionic liquids as a function of temperature
J. Chem. Eng. Data
Effect of temperature and composition on the transport and thermodynamic properties of binary mixtures of ionic liquid N-butyl-N-methylpyrrolidinium bis-(Trifluoromethanesulfonyl)imide and propylene carbonate
J. Sol. Chem.
Thermal conductivities of ionic liquids over the temperature range from 293 to 353 K
J. Chem. Eng. Data
Density and viscosity data for mixtures of ionic liquids with a common anion
J. Chem. Eng. Data
Ultrasonic and volumetric properties of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid with 2-propanol or tetrahydrofuran at several temperatures
J. Chem. Eng. Data
Ionic liquids: innovative fluids for chemical processing
AIChE J.
On the structure and dynamics of ionic liquids
J. Phys. Chem. B
Molecular simulation study of some thermophysical and transport properties of triazolium-based ionic liquids
J. Phys. Chem. B
Density and viscosity of several pure and water-saturated ionic liquids
Green Chem.
Cited by (20)
Volume fraction based Hind-Ubbelohde approach predicts viscosity with higher accuracy
2022, Journal of Molecular LiquidsCitation Excerpt :Keeping this in mind, the volume fractions of the constituent components would be a more appropriate component in the predictive equation as a substitution for the mole fraction, to the best of our knowledge. The modified HU equation has been tested on 196 binary, 13 ternary and 5 quaternary mixtures at varying temperatures [2,14–70] comprising of a large number of organic liquids like p-methyl Acetophenone, Octanol, Acetone, Nonane, Triethylamine, 2-Ethoxyethanol, Dioxane, Di-n-Butylamine, JP 10, etc. with diverse properties to check the robustness of the proposed approach. Also, the study has been extended to the ionic liquid likes [Bmim][NTf2], [eOHmim][BF4], [Bmim][BF4], [C4C1im][SCN], [C4C1im][CH3CO2], [C4C1im][(CH3O)2PO2] being one of the components in a binary liquid mixture and also IL + IL mixtures at varying temperatures.
Viscosity of [C<inf>4</inf>mim][(CF<inf>3</inf>SO<inf>2</inf>)<inf>2</inf>N], [C<inf>4</inf>mim][N(CN)<inf>2</inf>], [C<inf>2</inf>mim][C<inf>2</inf>H<inf>5</inf>SO<inf>4</inf>] and [Aliquat][N(CN)<inf>2</inf>] in a wide temperature range. Measurement, correlation, and interpretation
2021, Journal of Molecular LiquidsCitation Excerpt :This figure shows that several data sets have positive deviations in relation to our data, as high as + 8% at the lower temperatures. This might be an artifact for temperatures below 283 K, the lower limit of the VFT correlation, extrapolated down to 255 K. However, some data have negative deviations, and other with excellent agreement with our data, to within ± 2%, cases of Pereiro et al. (2012) [29], Fernandez et al. (2008) [30], Pinto et al. (2014) [31] and Anwar and Riyazuddeen (2017) [32], and some data, for temperatures 310 K of other authors. Deviations from our Vogel-Fulcher-Tammann equation (VFT) fit for the “water-free” values, reported in Table 2, are shown in Fig. 8.
A fresh look at the Hind Ubbelohde approach: Simple yet effective modification
2021, Journal of Molecular LiquidsCitation Excerpt :The newly developed approach has been put to test on 170 binary, 20 ternary and 6 quaternary systems across a range of temperatures. The experimental data for the comparative study of viscosity has been taken from literature [8–59]. Viscosity presents precious insights into the structural aspects and the interactions prevalent in the two and higher order mixture solvents and is vital to the evaluation of heat transfer and mass transport processes operations thereby aiding numerous design applications.